褐色聚合氮化碳纳米线双极光催化体系实现生物多元醇氧化与CO2还原协同产CO

doi:10.1016/S1872-2067(25)64928-X

摘要/Abstract

摘要： 一氧化碳(CO)是重要的化工合成中间体和能源载体, 传统制备途径依赖煤炭或甲烷蒸汽重整, 不仅能耗高且伴随大量碳排放. 相比之下, 利用生物质替代化石资源生产CO, 不仅可实现碳中和, 也契合可再生能源驱动的绿色化工方向. 生物多元醇是生物质转化的重要平台分子, 其光催化脱羰反应能够在温和条件下生成CO. 然而, 现有体系普遍需强碱或紫外光激发, 难以在可见光条件下高效进行. 同时, 生物多元醇氧化常伴随副产H₂的生成, 降低CO纯度. 若能将该氧化过程与CO₂还原反应偶联, 不仅可消耗氢源, 提高CO产率, 还能实现碳资源的循环利用. 因此, 构建在可见光驱动下可同步实现生物多元醇脱羰与CO₂还原的“双极光催化CO生成体系”具有重要的科学意义与应用价值.
本文通过调控聚合氮化碳(CN)的能带结构与光吸收特性, 成功制备出具有宽光谱响应的褐色聚合氮化碳纳米线(CNW), 并构建了在无碱、无金属、室温条件下运行的双极光催化CO生成体系. CNW由三聚氰胺、三聚氯氰及氰尿酸经溶剂热-热解法合成. 氧元素的引入有效破坏了七嗪结构单元的对称性, 导致电子结构重新分布, 使CNW的光吸收边拓展至约740 nm. 与未掺杂的CN相比, CNW的带隙由2.76 eV缩窄至1.91 eV, 但其价带与导带位置依然适宜于同时驱动CO₂还原与醇类氧化反应. 稳态荧光光谱、瞬态荧光光谱、飞秒瞬态吸收谱以及电化学阻抗分析表明, CNW具有更高的电子-空穴分离效率与载流子迁移能力, 即使在长波(λ > 700 nm)光辐照下, 仍能产生明显的光电流. 在以甘油为模型底物、CO₂饱和的体系中, CNW在全光谱照射下可实现724 μmol g^‒1 CO生成速率和99%的CO纯度, 活性较未掺杂CN提高3.4倍; 在λ > 420 nm可见光辐照条件下, CNW的CO产率是CN的7.1倍. 且CNW在长波(λ > 700 nm)光辐照下仍保持活性. ¹³CO₂同位素标记实验确认CO产物来源于甘油氧化与CO₂还原的双路径. 该双极光催化CO生成体系对多种生物多元醇(乙醇、葡萄糖、果糖和半乳糖等)均展现出良好的底物适应性. 机理研究显示, 光生空穴氧化甘油经醛中间体发生脱羰反应生成CO, 光生电子将CO₂还原为CO. 原位红外与密度泛函理论计算进一步揭示, 相比于CN, 氧掺杂CNW增强了CO₂吸附与活化能力, 降低了CO₂* → COOH* → CO* → CO反应路径的能垒; 同时, 甘油分子在氧掺杂的CNW表面的吸附与活化更为容易. 由此构建的双极反应体系实现了光生电子用于CO₂还原, 光生空穴用于生物醇氧化的协同产CO机制, 在无碱、无金属条件下实现了高效的宽光谱太阳能转化.
综上, 本研究报道了基于氧掺杂聚合氮化碳纳米线的双极光催化体系, 为实现宽光谱辐照的生物质与CO₂协同转化提供了新思路. 该体系突破了传统金属催化剂限制, 为构建宽光谱响应的非金属光催化剂体系及实现碳中和化学转化提供了重要参考. 未来可通过界面耦合与异质结设计进一步提升光生载流子利用效率, 推动太阳能驱动碳循环化学的发展.

关键词: 双极CO生成体系, 生物多元醇氧化, 光催化CO₂还原, 褐色聚合氮化碳纳米线

Abstract: Harnessing a single system capable of both oxidizing biopolyols and reducing carbon dioxide (CO₂) into carbon monoxide (CO) provides a sustainable pathway for simultaneous biomass conversion and CO₂ reduction. Traditional systems, however, are often limited by sluggish kinetics, requiring UV light or strongly alkaline media, which hampers their applicability under mild, visible-light conditions. In this study, we report an alkali- and metal-free photocatalytic CO production system operating at ambient temperature, employing brown polymeric carbon nitride nanowires (CNW) as the sole photocatalyst. The extended light-harvesting capacity of CNW enables efficient activity even under long-wavelength irradiation beyond 700 nm. The reaction pathways for biopolyol oxidative decarbonylation and CO₂-to-CO reduction were elucidated through a combination of in-situ spectroscopy and theoretical calculations. This visible-light-responsive dual-reaction platform directs photogenerated holes toward biopolyol oxidation and electrons toward CO₂ reduction, achieving efficient CO generation from renewable resources under mild conditions.

Key words: Bipolar CO production system, Biopolyols oxidation, Photocatalytic CO₂ reduction, Brown polymeric carbon nitride, nanowire

陈杨林, 方瑞明, 赵慧博, 封敏君, 侯卫东, TzeChienSum, WenLiu, 王亮, LydiaHelenaWong, 薛灿. 褐色聚合氮化碳纳米线双极光催化体系实现生物多元醇氧化与CO₂还原协同产CO[J]. 催化学报, DOI: 10.1016/S1872-2067(25)64928-X.

Yanglin Chen, Ruiming Fang, Huibo Zhao, Minjun Feng, Weidong Hou, Tze Chien Sum, Wen Liu, Liang Wang, Lydia Helena Wong, Can Xue. Bipolar photocatalysis for CO generation via biopolyol oxidation and CO₂ reduction over brown polymeric carbon nitride nanowires[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(25)64928-X.

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褐色聚合氮化碳纳米线双极光催化体系实现生物多元醇氧化与CO₂还原协同产CO

Bipolar photocatalysis for CO generation via biopolyol oxidation and CO₂ reduction over brown polymeric carbon nitride nanowires

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